CN101984749B

CN101984749B - Low-energy 4-cell electrochemical system with carbon dioxide gas

Info

Publication number: CN101984749B
Application number: CN200980101611.2A
Authority: CN
Inventors: R·J·吉利亚姆; T·A·阿尔布雷希特; N·贾拉尼; N·A·克诺特; V·德克; M·科斯托斯基; B·博格斯; K·法萨; A·高若尔
Original assignee: Calera Corp
Current assignee: Arilake
Priority date: 2008-07-16
Filing date: 2009-06-24
Publication date: 2015-02-18
Anticipated expiration: 2029-06-24
Also published as: AU2009271304B2; US7875163B2; CA2700721C; US20100116683A1; CA2700721A1; WO2010008896A1; AU2009271304A1; CN104722466A; EP2212033A4; CN101984749A; EP2212033A1; JP2011528405A

Abstract

A low-voltage, low-energy electrochemical system and method of producing hydroxide ions and/or bicarbonate ions and/or carbonate ions utilizing significantly less than the typical 3V used across the conventional anode and cathode to produce the ions; consequently, carbon dioxide emissions attributable to the present system and method are significantly reduced.

Description

Use the low-yield 4-battery electrochemical system of carbon dioxide

to the cross reference of related application

According to 35U.S.C. § 119 (e), this application claims the name submitted on July 16th, 2008 to be called: the U.S. Provisional Patent Application no.61/081 of the common transfer of " Low Energy pH Modulation for Carbon Sequestration UsingHydrogen Absorptive Metal Catalysts (using the low-yield pH of the carbon sequestration of hydrogen absorbability metallic catalyst to regulate) ", 299; Be called with the name that on August 25th, 2008 submits to: the U.S. Provisional Patent Application no.61/091 of the common transfer of " Low Energy Absorption ofHydrogenIon from an Electrolyte Solution into a Solid Material (hydrogen ion absorbs solid material from electrolyte solution is low-yield) ", the priority of 729, all the full text is incorporated herein by reference for both.

According to 35U.S.C. § 119 (a) with according to 35U.S.C. § 365, this application claims the PCT patent application no.PCT/US08/88242 that the name submitted on December 23rd, 2008 is called the common transfer of " Low Energy Electrochemical HydroxideSystem and Method (the oxide based method of unifying of low-yield electrochemical hydrogen) "; Be called the priority of the PCT patent application no.PCT/US09/32301 of the common transfer of " Low Energy Electrochemical Bicarbonate Ion Solution (low-yield electrochemical bicarbonate ion solution) " with the name submitted on January 28th, 2009, all the full text is incorporated herein by reference for both.

Background

Usually need the solution of hydroxyl ion, carbanion and/or bicarbonate ion with from solution except deprotonation, or the pH value of cushioning liquid, or precipitate insoluble hydroxide and/or carbonate and/or bicarbonate from solution.Traditionally, can by the quick lime of hydrolysising alkali such as slaking; Or produce hydroxyl ion by electrolysed saline solution obtained such as electrolytic sodium chloride aqueous solution (as in chloralkali process).Traditionally, carbanion or bicarbonate ion can be produced by being dissolved in by carbon dioxide in water or by solvable carbonate or bicarbonate such as sodium acid carbonate being dissolved in water.

Although hydrolysising alkali or electrolysed saline solution obtained can produce hydroxyl ion, the traditional mode of production lot of energy of hydroxyl ion; Great amount of carbon dioxide is also discharged in environment by this conventional method.Therefore, such as, in the production of quick lime, a large amount of fossil fuel that burns changes into calcium oxide with calcined limestone with by lime stone, and result great amount of carbon dioxide is discharged in environment.Similarly, when producing hydroxyl ion by chloralkali process, to drive this reaction, employ large energy owing to needing usually at least 3V between the anode and cathode.Because this energy is usually from the power plant that fossil fuels, this technique also causes great amount of carbon dioxide to be discharged in environment.Similarly, when by carbon dioxide solubility being produced in aqueous solution carbanion and bicarbonate ion, need quite a large amount of energy by this gas pressurized to improve solubility, result is due to energy used, and great amount of carbon dioxide is discharged in environment.Therefore, the high efficiency energy being starved of hydroxyl ion, carbanion and bicarbonate ion is produced.

General introduction

In various embodiments, native system and method relate to production hydroxyl ion and/or the low-voltage of bicarbonate ion and/or carbanion, low-yield electro-chemical systems and method.In various embodiments, this system and method utilizes the voltage being starkly lower than the general 3V used between conventional anode and negative electrode to produce ion; Therefore, the CO2 emission that native system and method cause obviously reduces.

In one embodiment, this system comprises: with the first electrolyte of cathode contacts; With the second electrolyte of positive contact; By the 3rd electrolyte that the first amberplex and the first electrolyte separate; By the 4th electrolyte that the second amberplex and the second electrolyte separate; With separate the third and fourth electrolytical 3rd amberplex.

In one embodiment, the method comprises: with cathode contacts settle the first electrolyte; With positive contact settle the second electrolyte; The 3rd electrolyte is settled to be separated by the first amberplex and the first electrolyte to make it; The 4th electrolyte is settled to separate to make it by the 3rd amberplex and the 3rd electrolyte and separated by the second amberplex and the second electrolyte; In the first electrolyte, hydroxyl ion is formed with by applying voltage between the anode and cathode.

In another embodiment, the method comprises: with cathode contacts settle the first electrolyte; With positive contact settle the second electrolyte; The 3rd electrolyte is settled to be separated by the first amberplex and the first electrolyte to make it; The 4th electrolyte is settled to separate to make it by the 3rd amberplex and the 3rd electrolyte and separated by the second amberplex and the second electrolyte; Carbon dioxide is supplied with to the first electrolyte.

In various embodiments, the first amberplex comprises cation-exchange membrane; Second amberplex comprises cation-exchange membrane; Anion-exchange membrane is comprised with the 3rd amberplex.In various embodiments, the first electrolyte is the catholyte with cathode contacts, and the second electrolyte is the anodolyte with positive contact.

In various embodiments, this system and method is applicable to via outflow stream Extraction parts or all catholytes and/or supplements this electrolyte via the inflow stream of this catholyte compartment.In various embodiments, this system and method is applicable to from outflow stream Extraction parts or all 4th electrolyte and supplements this electrolyte via the inflow stream of the 4th electrolyte compartment.In various embodiments, this system and method is applicable in batches, semi-batch or Continuous Flow operation, with or with extracting and supplementing the electrolyte in this system.

In various embodiments, this system comprises the hydrogen transfer system of the hydrogen guiding anode being applicable to negative electrode place to generate.In another embodiment, this system comprises carbon dioxide induction system, and it is applicable to carbon dioxide to be transported in catholyte, dissolves and may form bicarbonate radical and/or carbanion according to this electrolytical pH value this its.By being come by this gas dissolution in the embodiment of catholyte supply carbon dioxide in catholyte, this dissolving can flowed out in stream or occur flowing in stream or in one or more compartments between them in some embodiments.In various embodiments, this system is connected to the Industry Waste air-flow that comprises burning gases effectively with to this catholyte supply gas such as carbon dioxide.In various embodiments, this waste gas streams comprise fuel from fossil power plant, cement production plants and/or other factory burning gases.In various embodiments, this waste gas comprises sour gas, such as nitrogen oxide (nitrous oxide, nitric oxide) and sulphur gas (sulfur dioxide, hydrogen sulfide), and it dissolves and forms anion in this catholyte.In some embodiments, at this waste gas of the pre-treatment contacted with catholyte to remove the part or all of of its not carbon dioxide component.

In various embodiments, the product of this system and method, comprise hydroxyl ion, bicarbonate ion, carbanion, hydrochloric acid and therefrom eliminate the partially desalted water of some cation and anion, the U.S. Patent application no.12/344 of the common transfer that the 24 days December in 2008 as the full text is incorporated herein by reference submits to, described in 019, for by make waste gas with comprise bivalent cation and hydroxyl, the solution contact of bicarbonate radical and/or carbanion carrys out other composition of sequestration of carbon dioxide and industrial waste gas with precipitated carbonate and bicarbonate, such as sulphur gas, oxides of nitrogen gas and other burning gases.The sediment of the carbonate and bicarbonate that comprise such as calcium and magnesium is used as construction material in various embodiments, such as be used as cement and gather materials, the U.S. Patent application no.12/126 of the common transfer that 23 days Mays in 2008 as the full text is incorporated herein by reference submit to, described in 776.

In another purposes, therefrom eliminate the partially desalted water of cation and anion, the partially desalted water such as formed by removing sodium ion and chlorion from the 3rd electrolyte is used as the feed water in desalination system, at this U.S. Patent application no.12/163 as the common transfer submitted in the 27 days June in 2008 that the full text is incorporated herein by reference, this water of processing further described in 205.

In another embodiment, the acid of making in the 4th electrolyte and/or the aqueous slkali made in catholyte for dissolving the mineral and waste material that comprise bivalent cation such as Ca++ and Mg++, to produce the bivalent cation solution used when using this catholyte to manufacture bivalent metal ion carbonate sediment.In various embodiments, this sediment is used as construction material, such as cement and gathering materials, as the U.S. Patent application no.12/126 of the common transfer that the full text is incorporated herein by reference, described in 776.

Accompanying drawing is sketched

Following accompanying drawing property for example and not limitation sets forth the embodiment of native system and method.

Fig. 1 is the diagram of an embodiment of native system.

Fig. 2 is the flow chart of an embodiment of this method.

Fig. 3 is the flow chart of an embodiment of this method.

Describe in detail

Before detailed description this method and system, it should be understood that native system and method are not limited to the specific embodiments describing and exemplify herein, therefore variable.It is also to be understood that, term used herein only for describing specific embodiments and be not restrictive because its scope is only by the restriction of appended claims.

In this article, when providing number range, it should be understood that, each value (unless indicated separately clearly in literary composition, with 1/10 of the unit of lower limit for interval) between two parties between the upper and lower bound of this scope and other designated value any in this specified scope or between two parties value are included in native system and method.Except except any boundary value clearly got rid of in this specified scope, these upper and lower bounds more among a small circle can be included in independently these more among a small circle in and be also contained in the present invention.If this specified scope comprise one of boundary value or both, get rid of the arbitrary of these boundary values comprised or both scopes are also included within native system and method.

In this article, when the scope of description, the front term of numerical value " approximately " is modified.Term " approximately " is in this article for providing literal support for exact numerical values recited thereafter and the numerical value close or approximate with the numerical value after this term.When determining that whether a numerical value is close or be similar to the numerical value clearly enumerated, the close or approximate numerical value do not enumerated can be at the numerical value that it states in background and the numerical value clearly enumerated is substantially equivalent.

Unless otherwise specified, all technology used herein have the implication identical with the usual understanding of those skilled in the art with scientific and technical terminology.Implement native system and method although also can use with those similar or equivalent any method, system and materials described herein, only describe representational method, system and material in this article.

The all open source literatures quoted in this description and patent are all incorporated herein by this reference, just as each open source literature or patent are clear and definite and be specified one by one and be incorporated herein by this reference, be incorporated herein by this reference with in order to the disclosure and description method relevant to the open source literature quoted and/or material.Quoting of any open source literature is submitting disclosure a few days ago to for it, and should not be regarded as admitting that the present invention haves no right with preferred invention prior to the disclosure document.In addition, the publication date provided may be different from actual publication date, and this may need to confirm one by one.

Unless indicated separately clearly in literary composition, herein and singulative " a " used in claims, " an " and " the " comprise plural reference.Claims also may be drafted in a row except any optional key element.Therefore, this statement is intended to the antecedent basis serving as the use limited with the use enumerating the exclusiveness term as " only ", " only " and so on of coupling or " negativity " of claim elements.

Those skilled in the art can find out, each embodiment describing herein and exemplify has discrete component and feature, and they can easily separate with the feature of other several embodiment any in the case without departing from the scope of the present invention or combine.Any method enumerated can be carried out with cited event order or carry out with any order feasible in logic.

In various embodiments, native system and method relate to and manufacture hydroxyl ion and/or bicarbonate radical and/or carbanion in aqueous by low-voltage, low-yield electrochemical method.In one embodiment with reference to Fig. 1, by applying the voltage lower than 3V between negative electrode 104 and anode 108, in catholyte 102, produce hydroxyl ion, simultaneously: i) at anode 108 place, oxidation of hydrogen is produced proton; Ii) make proton from anode 108 via anodolyte 106 with move to the 4th electrolyte 116 through the second cation-exchange membrane 118; Iii) voltage between anode 108 and negative electrode 104 is made to remain the level not forming gas at anode 108 place; Iv) at negative electrode 104 place reductive water to form hydroxyl ion and hydrogen; V) by settling the first cation-exchange membrane 112 between catholyte 102 and the 3rd electrolyte 110, the hydroxyl ion in catholyte 102 is stoped to move to the 3rd adjacent electrolyte 110 from catholyte 102; Vi) make sodium ion move to catholyte 102 from the 3rd electrolyte 110, at this, they are combined to form NaOH in catholyte 102 with hydroxyl ion; Vii) make chlorion move to the 4th electrolyte 116 from the 3rd electrolyte 110 through anion-exchange membrane 120, at this, they merge with the proton moved from anode 108 and form hydrochloric acid; And vii) with the second cation-exchange membrane 118, anodolyte 106 and the 4th electrolyte 116 are separated.

In various embodiments, by the hydrogen guiding anode obtained at negative electrode place, at this by this gaseous oxidation.In various embodiments, from this system, (continually) takes out the NaOH made in catholyte and the hydrochloric acid made in the 4th electrolyte every now and then, runs every now and then with the sodium chloride that water supplements in this catholyte and the 3rd electrolyte with the continuous seepage maintaining this system simultaneously.In other embodiments, this system and method is applicable to other operational mode, such as in batches or semi-batch flow process (flow).

In another embodiment, neutralizing by carbon dioxide being dissolved in catholyte the voltage applied between the anode and the cathode lower than 3V, in this catholyte, manufacturing bicarbonate ion and/or carbanion.Carbon dioxide can be dissolved in catholyte and maybe can be dissolved in independent carbon dioxide compartment 152, and this carbon dioxide compartment is connected to catholyte compartment 122 to provide dissolving carbon dioxide in the solution to this catholyte compartment.In this embodiment, due to by carbon dioxide solubility in catholyte, following there are three kinds of reactions:

2H ₂O+2e ^-＝H ₂+2OH ^-

(water is in the reduction of negative electrode place)

H ₂O+CO ₂＝H ₂CO ₃＝H ⁺+HCO ₃ ^-＝H ⁺+CO ₃ ^2-

(according to this electrolytical pH value, in catholyte, forming carbonate and/or bicarbonate ion), and

H ⁺+OH ^--＞H ₂O

Because these reactions depend on pH, overall cathode reaction is:

2H ₂O+2CO ₂+2e ^-＝H ₂+2HCO ₃ ^-，

Or H ₂o+CO ₂+ 2e ^-=H ₂+ CO ₃ ^2-

Or the combination of these two kinds reactions, this depends on the pH of this catholyte.

In this embodiment with reference to Fig. 1, in catholyte 102, manufacture bicarbonate ion and/or carbanion by the voltage applied between negative electrode 104 and anode 108 lower than 3V, simultaneously: i) at anode 108 place by oxidation of hydrogen with anode 108 place produce proton; Ii) proton 108 making anode place be formed is from anode 108 via anodolyte 106 with move to the 4th electrolyte 116 through the second cation-exchange membrane 118; Iii) between anode 108 and negative electrode 104, voltage is applied not form gas at anode 108 place; Iv) manufacture hydrogen at negative electrode 104 place and optionally make this gas be circulated to anode 108; V) by settling the first cation-exchange membrane 112 between catholyte 102 and the 3rd electrolyte 110, the carbanion that prevention is made in catholyte 102 and/or bicarbonate anion move in the 3rd adjacent electrolyte 110, wherein select this cation-exchange membrane to move from catholyte 102 to stop anion; Vi) sodium ion is made to move to catholyte 102 from the 3rd electrolyte 110 through the first cation-exchange membrane 112; Vii) in catholyte 102, sodium ion is made to be combined to form sodium carbonate and/or sodium acid carbonate in this catholyte 102 with carbanion and/or bicarbonate ion; Viii) chlorion is made to move to the 4th electrolyte 116 from the 3rd electrolyte 110 through anion-exchange membrane 120; Ix) in the 4th electrolyte 116, chlorion is combined with the proton moved from anodolyte 106 and forms hydrochloric acid; And x) by settling the second cation-exchange membrane between the 4th electrolyte 116 and anodolyte 106, stop chlorion to move to anodolyte 106 from the 4th electrolyte 116, wherein select the second cation-exchange membrane 118 to move to anodolyte 106 from the 4th electrolyte 116 to stop anion.

In this embodiment of this system, as the embodiment of above-mentioned manufacture hydroxyl ion, the hydrogen guiding anode optionally produced at negative electrode place, is oxidized at this, or is discharged this gas.In the embodiment of discharging hydrogen, another sources of hydrogen anode provides hydrogen.In the various embodiments of this system, as the production of hydroxyl ion, the carbanion made in catholyte and/or bicarbonate ion is frequently taken out, with often supplementing sodium chloride in this catholyte and the 3rd electrolyte to maintain the continuous operation of this system with water from this system.In various embodiments, this system and method is applicable to other operational mode, such as in batches or semi-batch flow process.

In various embodiments, those of ordinary skill in the art will appreciate that, the voltage between anode and negative electrode depends on that the pH between the pH value of anodolyte and catholyte and these electrolyte is poor.Therefore, in various embodiments, when the voltage applied between the anode and cathode is lower than 3,2.9,2.8,2.7,2.6,2.5,2.4,2.3,2.2,2.1,2.0,1.9,1.8,1.7,1.6,1.5,1.4,1.3,1.2,1.1,1.0,0.9,0.8,0.7,0.6,0.5,0.4,0.3,0.2 or 0.1V or lower, the pH difference between anodolyte and catholyte is 0,1,2,3,4,5,6,7,8,9,10,11,12,13,14pH unit or larger while; With the pH value at this anodolyte from 1 to 7pH unit change and the pH value of this catholyte be 7 to 14pH unit or larger while, in catholyte, produce hydroxyl ion, carbanion and/or bicarbonate ion.

In various embodiments with reference to Fig. 1, by arrangement second cation-exchange membrane 118 selective between anodolyte 106 and the 4th electrolyte 116, when applying voltage of the present invention between anode 108 and negative electrode 104, the protolysis formed by oxidation of hydrogen at anode 108 place is in anodolyte 106, and they move in the 4th electrolyte 116 through the second cation-exchange membrane 118 from here.But, because the 4th electrolyte 116 and the 3rd electrolyte 110 are separated by anion-exchange membrane 120, stop proton to move further to negative electrode from the 4th electrolyte 116 through the 3rd electrolyte 110; Therefore, proton accumulates in form acid in the 4th electrolyte 116, such as hydrochloric acid.

Similarly, with reference to Fig. 1, by arrangement first cation-exchange membrane 112 selective between catholyte 102 and the 3rd electrolyte 110, when applying low-voltage between anode 108 and negative electrode 104, in catholyte 102, form hydroxyl ion or carbanion or bicarbonate ion, stop them to move to from here in the 3rd electrolyte 110 with the first cation-exchange membrane 112.Therefore, hydroxyl ion or carbanion or bicarbonate ion are included in catholyte 102.Meanwhile, the hydrogen formed at negative electrode 104 place by the water reduction of negative electrode 104 is discharged or leads anode to be oxidized this gas at anode place.If discharge this hydrogen, then other external source hydrogen source anode is used to provide hydrogen.

In various embodiments with reference to Fig. 1, because the first cation-exchange membrane 112 allows cation to move to catholyte 102 and anion-exchange membrane 120 allows anion to move to the 4th electrolyte 116 from the 3rd electrolyte 110 from the 3rd electrolyte 110, when applying voltage between the anode and cathode, cation, such as sodium ion to move to catholyte 102 and anion from the 3rd electrolyte 110, and such as chlorion can move to the 4th electrolyte 116 from the 3rd electrolyte 110.

Therefore, at the 3rd electrolyte 110 at first containing in the embodiment of sodium chloride, sodium ion can from the 3rd electrolyte to catholyte 102 to form NaOH or sodium acid carbonate or sodium carbonate according to the pH value of catholyte 102.Similarly, chlorion can move to the 4th electrolyte from the 3rd electrolyte 110, thus forms hydrochloric acid 148 with the proton moved from anodolyte 106.Therefore, in various embodiments, in the 3rd electrolyte 110, create the partially desalted water 150 from wherein eliminating sodium ion and chlorion.

Hydrogen is not used in the various embodiments of anode place oxidation wherein, this system and method is applicable in catholyte, produce hydroxyl, bicarbonate radical and carbanion and produce gas at anode place, such as oxygen or chlorine while negative electrode place produces hydrogen.As other embodiment, in this embodiment, this system and method is applicable to while anode place forms gas such as oxygen or chlorine, forms acid and forming section desalted water in the 3rd electrolyte in the 4th electrolyte.But, in this embodiment, due to hydrogen not anode place oxidation, usually need between a cathode and an anode more high voltage to drive the electrochemical reaction in this system.

In various embodiments with reference to Fig. 1, voltage as described herein is applied by between negative electrode 104 and anode 108, formed at anode place and to move in anodolyte 106 and move to the proton in the 4th electrolyte 116 through the second cation-exchange membrane 118, the pH of anodolyte 106 and the 4th electrolyte 116 can be regulated according to the electrolyte flow flowing through this system.Simultaneously, owing to preventing hydroxyl ion, bicarbonate ion or the carbanion formed in catholyte 102 from moving from this catholyte through the first cation-exchange membrane, the pH of catholyte 102 can be regulated according to the electrolyte flow flowing through this system.Therefore, in various embodiments, pH is obtained poor between catholyte 102 and anodolyte 106, such as, according to flowing through the electrolyte flow of this system, at least 1,2,3,4,5,6,7,8,9,10,11,12,13 or 14pH unit or larger difference.Similarly, because proton moves to the 4th electrolyte 116 from anodolyte 106, pH is obtained poor between the 4th electrolyte 116 and catholyte 102, such as according to flowing through the electrolyte flow of this system, at least 1,2,3,4,5,6,7,8,9,10,11,12,13 or 14pH unit or larger difference.

In the following exemplary description of the specific embodiments of this system and method, for illustrating, system constructs as in figure 1, wherein uses the concentrated sodium chloride aqueous solution 142 as initial 3rd electrolyte 110 between the first cation-exchange membrane 112 and anion-exchange membrane 120.Also within the system, use conductivity water or low-concentration sodium hydroxide solution or sodium bicarbonate solution or sodium carbonate liquor as initial catholyte 102; Within the system, use conductivity water as anodolyte 106; Still within the system, use the low-concentration hcl made in the 4th electrolyte 116 as initial 4th electrolyte.

Therefore, within the system, when applying voltage between anode 108 and negative electrode 104, sodium ion moves to catholyte 102 from the 3rd electrolyte 110, and chlorion is from the 3rd electrolyte to the 4th electrolyte 116; (depend on and whether carbon dioxide is added in electrolyte) in catholyte 102 and produce hydroxyl ion or carbanion or bicarbonate ion; Hydrogen is produced at negative electrode 104 place; The hydrogen that anode 108 is supplied is oxidized to proton at anode place; And this protolysis is in anodolyte 106, they move in the 4th electrolyte 116 through the second cation-exchange membrane 118 from here, and because anion-exchange membrane 120 can stop them to move to further in the 3rd electrolyte 110, they accumulate in herein.

Therefore, in various embodiments, when applying voltage between the anode and cathode, within the system, in catholyte, NaOH is produced; Hydrochloric acid is produced in the 4th electrolyte; The concentration of the sodium chloride in the 3rd electrolyte reduces; Hydrogen is oxidized at anode place; And generate hydrogen at negative electrode place.

In an embodiment of this system---be wherein dissolved in catholyte by carbon dioxide, this system and method produces bicarbonate radical and/or carbanion in addition in catholyte; Therefore, in this embodiment, according to the pH value of this catholyte, in this catholyte, sodium acid carbonate and/or sodium carbonate is produced.In this embodiment, as not by the embodiment of carbon dioxide solubility in catholyte, this system and method produces hydrochloric acid in the 4th electrolyte; Sodium chloride concentration in 3rd electrolyte reduces; Hydrogen is oxidized at anode place; And generate hydrogen at negative electrode place.

Those of ordinary skill in the art will appreciate that, native system and method are not limited to sodium chloride solution as the 3rd electrolytical this exemplary purposes, but are applicable to use equal ion salt solution, such as potassium sulfate in the 3rd electrolyte.Therefore, such as, if use potassium sulfate, in the 4th electrolyte, produce sulfuric acid and in catholyte, produce potassium hydroxide, saleratus and/or potash.Can recognize, can come to produce proton at anode place by the hydrogen of oxidation anode supply using potassium sulfate as the 3rd this system and method electrolytical; Hydrogen is formed at negative electrode place; With remove the 3rd electrolytical potassium and sulfate ion.Carbon dioxide is being dissolved in the embodiment in catholyte, bicarbonate radical and carbanion can be being produced using potassium sulfate in catholyte as the 3rd this system and method electrolytical.Therefore, in this equivalent system, according to the pH value of this catholyte, in catholyte, produce potassium hydroxide, saleratus and/or potash.Can be used for other electrolyte electrolytical manufactured in native system and comprise seawater, brackish water and salt solution.This kind of equivalent system and method are therefore in the scope of native system and method.

Those skilled in the art also will appreciate that, by carbon dioxide solubility in catholyte to manufacture in the embodiment of bicarbonate radical and carbonate anion, in water react, dissolve and other equal gas Ionized can produce comparable results.Therefore, such as, dissolve in the sour gas of this catholyte as sulfur dioxide and nitrogen oxide, equal anion can be produced in this catholyte.Therefore, be dissolved in produce with regard to equal anion in the 3rd electrolyte as carbon dioxide with regard to equal gas, such system and method is also in the scope of native system and method.

In various embodiments, this system and method is applicable to part or all of catholyte to extract the inflow stream of cathodic compartment from outflow stream.This system and method is also applicable to part or all of 4th electrolyte to extract the 4th electrolytical inflow stream from outflow stream.In various embodiments, this system and method is applicable in batches, semi-batch or Continuous Flow operation, with or be not directed at the oxidation of anode place with the hydrogen generated at negative electrode place, and with or with extracting and supplementing the electrolyte in this system.

In various embodiments, this system comprises the hydrogen transfer system for making hydrogen from cathode circulation to anode.In another embodiment, this system comprises the carbon dioxide induction system for being dissolved in by carbon dioxide in catholyte.In various embodiments, this system is connected to the Industry Waste air-flow comprising burning gases effectively, with such as, to catholyte supply gas, carbon dioxide.In various embodiments, this waste gas streams comprises the burning gases from the power plant of fossil fuel energy supply, cement production plants and other factory.In various embodiments, this waste gas comprises sour gas, such as nitrogen oxide (nitrous oxide, nitric oxide) and sulphur gas (sulfur dioxide, hydrogen sulfide), it dissolves and forms anion in this catholyte, and this is similar to the generation of bicarbonate radical and carbanion when carbon dioxide solubility is in this catholyte.

With reference to Fig. 1, in one embodiment, system 100 comprises: the first electrolyte contacted with negative electrode 104, i.e. catholyte 102; The second electrolyte contacted with anode 108, i.e. anodolyte 106; By the 3rd electrolyte 110 that the first cation-exchange membrane 112 separates with catholyte 102; By the 4th electrolyte 116 that the second cation-exchange membrane 118 separates with anodolyte 106; By the 3rd amberplex 120 that the 3rd electrolyte 110 and the 4th electrolyte 116 separate.In various embodiments, the first amberplex comprises cation-exchange membrane; Second amberplex comprises cation-exchange membrane; And the 3rd amberplex comprises anion-exchange membrane.

In system in FIG, catholyte 102 is with negative electrode 104 fluid contact and be both contained in the first battery 122 limited by the first cation-exchange membrane 112 and the first side wall 124.Similarly, anodolyte 106 is both contained in the second battery 126 limited by the second cation-exchange membrane 118 and the second sidewall 128 with anode 108 fluid contact.The 3rd battery 130 of accommodation the 3rd electrolyte 110 is limited by the first cation-exchange membrane 112 and anion-exchange membrane 120; And the 4th battery 132 of accommodation the 4th electrolyte 116 is limited by anion-exchange membrane 120 and the second cation-exchange membrane 118.

Also with reference to Fig. 1, system 100 comprises in various embodiments can execute alive voltage source 134 between anode 108 and negative electrode 104.In various embodiments, the negative electrode in this system and anode by non-reacted conductive material, as nickel or platinum are formed.This system comprises the hydrogen being applicable to negative electrode 104 place is generated and circulates with the hydrogen gas circulating system 136 be oxidized at anode 108 place.In various embodiments, this hydrogen effectively can be connected to external hydrogen source of supply (not shown) and provide hydrogen with anode, such as when under-supply from the hydrogen of negative electrode at this operation start time provide.

In various embodiments, this system comprises the catholyte extraction and replenishment system 138 that are applicable to extract all or part of catholyte 102 from the first battery 122 holding catholyte.In various embodiments, this system comprises the 4th electrolyte extraction and the replenishment system 140 that are applicable to extract and supplement all or part of 4th electrolyte 116 to electrolytical 4th battery 132 of accommodation the 4th.In various embodiments, this system comprises the salt supply system for providing salting liquid 142 such as concentrated sodium chloride to the 3rd electrolytic cell 130.In various embodiments, this system comprises the gas supply system 144 for providing gas such as carbon dioxide to catholyte 102.In various embodiments, this system comprises carbon dioxide mix system 152, wherein by to flow out in stream or to flow in stream or in one or more compartments between them by this gas dissolution in negative electrode (electrolyte), to this catholyte supply carbon dioxide.In various embodiments, this system comprises for fluid being introduced the entrance (not shown) of battery (122,126,130,132) and the outlet (not shown) for removing fluid from battery.

In various operational mode, such as, in Continuous Flow, in batches stream or mixed mode, this system can produce sodium hydroxide solution 146 when being equipped with sodium chloride solution 142 in catholyte 102, in the 4th electrolyte 116, produce hydrochloric acid 148, and produce the partially desalted aqueous solution 150 of its cationic and anion-content reduction.In various embodiments, this partially desalted aqueous solution 150 is used as the feed water of Demineralized Water Production device (not shown) to process further, thus other ion existed in removing such as this solution.In other embodiments, this aqueous solution 150 is for the preparation of the initial electrolysis matter solution loading electrolyte in the first battery 122, second battery 126, the 3rd battery 130 and the 4th battery 132.

Can recognize, in various embodiments with reference to Fig. 1, although: i) with the first cation-exchange membrane 112, catholyte 102 and the 3rd electrolyte 110 are separated; And ii) with the second cation-exchange membrane 118, the 4th electrolyte 116 is separated with anodolyte 106; And iii) with anion-exchange membrane 120, the 4th electrolyte 116 and the 3rd electrolyte 110 are separated; But, when applying voltage 134 between anode 108 and negative electrode 104, electronegative anion in electrolyte is attempted (attempt) and is moved to positive anode 108, and the cation of positively charged is attempted to move to negative negative electrode 104 through the first cation-exchange membrane 112, second cation-exchange membrane 118 and anion-exchange membrane 120.

Therefore, for example, referring to Fig. 1, wherein first by respectively to adding a small amount of NaOH in electrolyte and hydrochloric acid makes catholyte 102 and anodolyte 106 conduct electricity; 4th electrolyte 116 is the aqueous solution, first makes it conduct electricity by being added in this solution by a small amount of hydrochloric acid; First sodium chloride concentrated solution is placed in the 3rd electrolyte 110; First hydrogen stream 136 is led anode 108 to be oxidized at anode 108 place via anodolyte 106, when applying voltage 134 between anode 108 and negative electrode 104, form proton at anode 108 place by the oxidation of the hydrogen 136 to this anode supply as follows, form hydroxyl ion and hydrogen 138 at catholyte 116 place by the reduction of water simultaneously:

H ₂=2H ⁺+ 2e ^-(anode, oxidation reaction)

2H ₂o+2e ^-=H ₂+ 2OH ^-(negative electrode, reduction reaction)

Those of ordinary skill in the art will appreciate that, with reference to Fig. 1, because the hydrogen 136 supplied by anode 108 at anode place 108 forms proton; And owing to not forming gas as oxygen at anode 108 place; And due to water in catholyte electrolysis to form hydroxyl ion and hydrogen 138 at negative electrode 104 place, therefore, when applying voltage between anode 108 and negative electrode 104, this system produces hydroxyl ion and produce proton in anodolyte 106 in catholyte 102.

In addition, those skilled in the art will recognize that, with generate compared with the higher voltage that needs in the legacy system of gas such as chlorine at anode place, in the present system, owing to not forming gas at anode place, when applying between the anode and cathode lower than 3V, this system can produce hydroxyl ion and produce hydrogen at anode place in catholyte.Such as, in various embodiments, when apply between the anode and cathode lower than lower than 2.0,1.5,1.4,1.3,1.2,1.1,1.0,0.9,0.8,0.7,0.6,0.5,0.4,0.3,0.2,0.1V or lower time, produce hydroxyl ion.

In addition, those of ordinary skill in the art will appreciate that, with reference to Fig. 1, when applying voltage between anode 108 and negative electrode 104, the proton of the positively charged formed at anode place is attempted to migrate to negative electrode 104 via anodolyte 106, and the electronegative hydroxyl ion simultaneously formed at negative electrode 104 place is attempted to migrate to anode 108 via catholyte 102.

But, as shown in fig. 1 with about the hydroxyl ion in catholyte 102, because catholyte 102 bag is contained in the first battery 122 by the first cation-exchange membrane 112, and stop anion to move to the 3rd electrolyte 110 from catholyte 102 due to the first cation-exchange membrane 112, the hydroxyl ion generated in catholyte 102 can be stoped to move out of catholyte through this first cation-exchange membrane 112.Therefore, when applying voltage 134 between the anode and cathode, the hydroxyl ion that negative electrode place produces is included in catholyte 102.Therefore, flow into according to fluid and flow out the flow velocity of catholyte, the pH of this catholyte adjustable, such as this pH can improve, reduces or keep identical.

Similarly, about the proton generated at anode 108 place, the applied voltage between negative electrode 104 and anode 108 134 times, this proton can enter anodolyte 106 and move in the 4th electrolyte through the second cation-exchange membrane 118.But, because the anion-exchange membrane 120 between the 4th electrolyte 116 and the 3rd electrolyte 110 stops cation to shift to the 3rd electrolyte 110 from the 4th electrolyte 116, therefore, prevent proton in the 4th electrolyte 116 from the 4th electrolyte to the 3rd electrolyte 110.Therefore, when applying voltage 134 between the anode and cathode, the proton that anode place produces is included in the 4th electrolyte 116.Therefore, flow into according to fluid and flow out the 4th electrolytical flow velocity, regulate the 4th electrolytical pH, such as this pH can improve, reduces or keep identical.

About initial concentrated solution containing sodium ion and chlorion and the 3rd electrolyte 110 sandwiched in the 3rd battery 130 by anion-exchange membrane 120 and the first cation-exchange membrane 112, when applying voltage between anode 108 and negative electrode 104, anion such as chlorion in 3rd electrolyte 110 is attempted anode 108 and is moved, and the 3rd electrolytical cat ions such as sodium ion is attempted to move to negative electrode 104.Because anion-exchange membrane 120 allows anion to move to the 4th electrolyte 116 from the 3rd electrolyte 110, the chlorion existed in the 3rd electrolyte 110 can move in the 4th electrolyte, and at this, they form acid, such as hydrochloric acid with the proton from anode.

In addition, because the first cation-exchange membrane 112 allows cation to move to catholyte 102 from the 3rd electrolyte 110, the sodium ion existed in 3rd electrolyte 110 can move in catholyte 102, and the hydroxyl ion that they can generate with negative electrode 104 place at this forms NaOH.Therefore, as shown in fig. 1, when applying voltage between anode 108 and negative electrode 104, cat ions is as sodium ion, and anion such as chlorion can move out from the 3rd electrolyte 110, forms desalted water thus in the 3rd electrolyte.

In various embodiments and as shown in fig. 1, hydrogen 120 is generated at negative electrode 104 place by the reduction of the water in catholyte.This gas can be discharged or guiding anode 108 from negative electrode, is as described hereinly oxidized to proton at this.

In other embodiments, according to desired ion thing class, can by other reactants dissolved in catholyte to manufacture desired ion.Therefore, such as, in various embodiments, carbon dioxide is added in catholyte to manufacture carbonate and bicarbonate ion.Carbon dioxide is by entering electrolyte to add in this electrolyte by its direct bubbling (bubbling); Or carbon dioxide can be dissolved in catholyte and maybe can be dissolved in independent compartment 152, the solution containing the carbon dioxide dissolved adds in this cathodic compartment to cathodic compartment with described above by this compartment tubes connection.

By in the embodiment of carbon dioxide solubility in catholyte, as mentioned above with reference to Fig. 1, when applying voltage between anode 108 and negative electrode 104, system 100 can produce hydroxyl ion, bicarbonate ion, carbanion and hydrogen as follows:

2H ₂o+2e ^-=H ₂+ 2OH ^-(water is in the reduction of negative electrode place)

In catholyte 102, according to electrolytical pH, carbon dioxide gas is known from experience following dissolving and is formed carbonic acid, proton, bicarbonate ion and carbanion:

H ₂O+CO ₂＝H ₂CO ₃＝H ⁺+HCO ₃ ^-＝2H ⁺+CO ₃ ^2-

Because the dissolving of carbon dioxide in catholyte 102 and the concentration dependant of bicarbonate radical and carbanion are in pH, the general reaction in first (negative electrode) battery 122 is:

Situation 1:2H ₂o+2CO ₂+ 2e ^-=H ₂+ 2HCO ₃ ^-; Or

Situation 2:H ₂o+CO ₂+ 2e ^-=H ₂+ CO ₃ ^2-

Or both combinations, as following carbonate species are formed as shown in figure, this depends on the pH of catholyte 102:

H ₂carbonate/bicarbonate species in O form the pH of vs. at 25 DEG C

For arbitrary situation, total cell voltage potential can be determined by following formula by the Gibbs energy change of this reaction:

E _battery=-Δ G/nF

Or, in standard temperature and pressure conditions:

E ° _battery=-Δ G °/nF

Wherein, E _batterybe cell voltage, Δ G is the Gibbs energy of this reaction, and n is the electron number of transfer, and F is Faraday constant (96485J/Vmol).These react respective E _batterypH is depended in the face of the Nernst equation shown in situation 1 according to following:

Situation 1: the bicarbonate ion in catholyte generates

For arbitrary situation, total cell voltage potential can be determined by the combination of the Nernst equation of each half-cell reaction:

E＝E°-RTln(Q)/nF

Wherein, E ° is normal reduction potential, and R is universal gas constant, and (8.314J/mol K) T is absolute temperature, and n is the electron number participating in this half-cell reaction, and F is Faraday constant (96485J/Vmol), and Q is reaction business, to make:

E _{total amount}=E _{negative electrode}+ E _anode

When hydrogen-oxygen being changed into proton at anode place as follows:

H ₂＝2H ⁺+2e ^-，

E ° is 0.00V, n is 2, and Q is H ⁺activity square, to make:

E _anode=-0.059pH _a,

Wherein pH _athe pH of anodolyte.

When water being reduced at negative electrode place hydroxyl ion and hydrogen as follows:

2H ₂O+2e ^-＝H ₂+2OH ^-，

E ° is-0.83V, n is 2, and Q is OH ^-activity square, to make:

E _{negative electrode}=-0.059pH _c,

Wherein pH _cthe pH of catholyte.

For arbitrary situation, the E of negative electrode and anode reaction with anode and catholyte pH and become.Therefore, for situation 1, if the anode reaction occurred in sour environment is in pH 0, then for this half-cell reaction, the E of this reaction is 0V.For cathode reaction, if the pH 7 that is created on of bicarbonate ion occurs, then for this half-cell reaction, theoretical E is 7x (0.059V)=0.413V, and wherein negative E means needs energy to be inputted this half-cell or whole battery proceeds to make this reaction.Therefore, if anode pH is 0 and negative electrode pH is 7, then total cell voltage potential is 0.413V, wherein:

E _{total amount}=0.059 (pH _a-pH _c)=0.059 Δ pH.

For situation 2, wherein produce carbanion, if anode pH is 0 and negative electrode pH is 10, this represents the E of 0.59V.

Therefore, in various embodiments, by CO ₂the effect importing catholyte (to reduce the pH of this catholyte and produce bicarbonate ion and/or carbanion in this catholyte) is reduced in this catholyte the voltage manufactured between the anode in system needed for hydroxide, carbonate and/or bicarbonate and negative electrode.In situation 1, can recognize, if make catholyte rise to the pH of 14 or larger, the difference of anodic half-cell electromotive force (being expressed as thin horizontal dotted line) and cathode half-cell electromotive force (being expressed as thick solid diagonal line) rises to 0.83V.Along with not adding CO ₂or the raising of battery operation duration when not having other to intervene such as dilute with water, required cell voltage potential continues to improve.Therefore can recognize, the electrochemical cell under the negative electrode pH of 7 or larger runs and significantly saves energy.

Therefore, those of ordinary skill in the art can recognize, for the different pH value in catholyte and anodolyte, when the voltage applied between the anode and cathode is lower than 3, 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2 or 0.1V or lower time, hydroxyl ion is produced in catholyte, carbanion and/or bicarbonate ion, pH difference simultaneously between anodolyte and catholyte is for being greater than 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or larger.

Those skilled in the art also will appreciate that, needing to manufacture in the embodiment of bicarbonate radical and/or carbanion, system as shown in fig. 1 and as described in the generation above with reference to hydroxyl ion is applicable to by applying lower than 3V by carbon dioxide solubility in catholyte 102 and between negative electrode 104 and anode 108, or lower than 2.5V, or lower than 2V, or in catholyte 102, manufacture bicarbonate ion and/or carbanion lower than the voltage of 1.5V, simultaneously: i) at anode 108 place by oxidation of hydrogen with anode 108 place produce proton; Ii) proton making anode 108 place be formed is from anode 108 via anodolyte 106 with move to the 4th electrolyte 116 through the second cation-exchange membrane 118; Iii) between anode 108 and negative electrode 104, voltage is applied not form gas at anode 108 place; Iv) manufacture hydrogen at negative electrode 104 place and optionally make this gas be circulated to anode 108; V) by settling the first cation-exchange membrane 112 between catholyte 102 and the 3rd electrolyte 110, the carbanion made in prevention catholyte 102 and/or bicarbonate anion move in adjacent 3rd electrolyte 110, wherein select this cation-exchange membrane to move from catholyte 102 to stop anion; Vi) sodium ion is made to move to catholyte 102 from the 3rd electrolyte 110 through the first cation-exchange membrane 112; Vii) in catholyte 102, sodium ion is made to be combined to form sodium carbonate and/or sodium acid carbonate at catholyte 102 with carbanion and/or bicarbonate ion; Viii) chlorion is made to move to the 4th electrolyte 116 from the 3rd electrolyte 110 through anion-exchange membrane 120; Ix) in the 4th electrolyte 116, chlorion is combined with the proton moved from anodolyte 106 and forms hydrochloric acid; And x) by settling the second cation-exchange membrane between the 4th electrolyte 116 and anodolyte 106, stop chlorion to move to anodolyte 106 from the 4th electrolyte 116, wherein select the second cation-exchange membrane 118 to move to anodolyte 106 from the 4th electrolyte 116 to stop anion.

Therefore, when manufacturing carbonate/bicarbonate ion in catholyte 102, as the above-mentioned embodiment manufacturing hydroxyl ion when not adding carbon dioxide in catholyte in catholyte, anode 108, first cation-exchange membrane 118, anion-exchange membrane 120, first cation-exchange membrane 112, anodolyte, the 4th electrolyte are functionally identical with the 3rd electrolyte.

As the generation of hydroxyl ion, carbonate and or bicarbonate radical generation in, the optional delivery of the hydrogen 136 produced at negative electrode 104 place is used for the oxidation of hydrogen at anode 108 place; From the 3rd electrolyte 110, obtain the desalted water 150 removing sodium chloride, and produce hydrochloric acid 148 in the 4th electrolyte.In addition, in various embodiments, as the generation of hydroxyl ion, can from this system every now and then (continually) take out the carbanion or bicarbonate ion made in catholyte, with often supplementing the water in this catholyte and the sodium chloride in the 3rd electrolyte to maintain the continuous operation of this system.In various embodiments, this system and method is applicable to other operational mode, such as in batches or semi-batch flow process.

Those skilled in the art will recognize that, in various embodiments, this system can be configured to various production model, comprise batch mode, semi-batch pattern, continuous flow mode operation, can to select or can not the NaOH made in catholyte of selective extraction part or extract all or part of acid of making in the 4th electrolyte, or by the hydrogen guiding anode of negative electrode place generation, can be oxidized at this.

In various embodiments, when the voltage applied between the anode and cathode is lower than 3, 2.9 or lower, 2.8 or lower, 2.7 or lower, 2.6 or lower, 2.5 or lower, 2.4 or lower, 2.3 or lower, 2.2 or lower, 2.1 or lower, 2.0 or lower, 1.9 or lower, 1.8 or lower, 1.7 or lower, 1.6 or lower, 1.5 or lower, 1.4 or lower, 1.3 or lower, 1.2 or lower, 1.1 or lower, 1.0 or lower, 0.9 or lower, 0.8 or lower, 0.7 or lower, 0.6 or lower, 0.5 or lower, 0.4 or lower, 0.3 or lower, 0.2 or lower, or during 0.1V or lower, hydroxyl ion is produced in catholyte, bicarbonate ion and/or carbanion solution.

In another embodiment, this system and method is applicable in catholyte, produce hydroxyl ion, carbanion and bicarbonate ion and while negative electrode place generates hydrogen, form gas, such as oxygen or chlorine at anode place.But, in this embodiment, not anode supply of hydrogen.Although can produce proton and produce NaOH, sodium carbonate and/or sodium acid carbonate in catholyte at anode place in this embodiment, the voltage between anode and negative electrode is usually above not forming gas at anode place but embodiment at anode place by oxidation of hydrogen.

In various embodiments with reference to Fig. 1, available anion-exchange membrane 120 comprises the amberplex that conventional anion exchanges.Preferably, this kind of film should can be used for about 0 DEG C to about 100 DEG C or higher acidity and/or alkaline electrolyte solution temperature.Similarly, the first cation-exchange membrane 112 and the second cation-exchange membrane 118 can be selected from common cationic exchange membrane and should can be used for about 0 DEG C to about 100 DEG C or higher acidity and/or alkaline electrolyte solution temperature.

The example of suitable cation-exchange membrane comprises such as can available from Asahi Kasei of Tokyo, the Teflon of Japan ^tM-basement membrane.Usually, Exemplary cationic exchange membrane should be able to be used in the strong alkali solution in about 0 DEG C extremely about 120 DEG C and higher temperature range.But, with reference to Fig. 1, can recognize, due to low-voltage and the cold operation of native system, also can adopt other low cost hydrocarbylphosphonium cations exchange membrane.This kind of hydrocarbon based membranes can available from such as Membrane Internationalof Glen Rock, NJ, USA.

Similarly, typical alkyl anion-exchange membrane also can available from Membrane Internationalof Glen Rock, NJ, USA.Usually, this series anion-exchange membrane should show high ion selectivity, low ion resistance, high bursting strength and the high stability in the acidic electrolysis solution temperature ranges of about 0 DEG C to about 100 DEG C or higher.

One skilled in the art will realize that, because cation-exchange membrane is optionally to make cation move between two kinds of adjacent electrolysis matter, time between the two kinds of electrolyte as shown in fig. 1 cation-exchange membrane being placed in electro-chemical systems, this film allows cation to move to adjacent electrolysis matter from a kind of electrolyte towards cathode direction.Such as, therefore, and with reference to Fig. 1, when applying voltage between negative electrode 104 and anode 108, cat ions, as sodium ion, can move to catholyte 102 from the 3rd electrolyte 110 through the first cation-exchange membrane 112.Also will appreciate that, meanwhile, anion can be stoped to move to the 3rd electrolyte 110 towards anode 108 direction from catholyte to the first cation-exchange membrane 112 of cation selective.

Those skilled in the art also will appreciate that, because anion-exchange membrane is optionally to make anion move between two kinds of adjacent electrolysis matter, time between the two kinds of electrolyte as shown in fig. 1 anion-exchange membrane being placed in electro-chemical systems, this film allows anion to move to adjacent electrolysis matter from a kind of electrolyte towards anode direction.

Therefore, such as, and with reference to Fig. 1, when applying voltage between negative electrode 104 and anode 108, anion is chlorion such as, can move to the 4th electrolyte 116 from the 3rd electrolyte 110 through anion-exchange membrane 120.Also will appreciate that, meanwhile, cation can be stoped to move to the 3rd electrolyte 110 towards negative electrode 104 direction from the 4th electrolyte 116 to the anion-exchange membrane 120 of anion selectivity.

With reference to Fig. 1 and 2, method 200 comprises step 202 in one embodiment: such as with cathode contacts settle the first electrolyte, i.e. catholyte, and with positive contact settle the second electrolyte, i.e. anodolyte; Such as settle the step 204 that the 3rd electrolyte is separated by the first cation-exchange membrane and catholyte to make it; Such as settle the step 206 that the 4th electrolyte is separated to make it by anion-exchange membrane and the 3rd electrolyte and separated by the second cation-exchange membrane and anodolyte; In catholyte, the step 208 of hydroxyl ion is such as formed by applying voltage between the anode and cathode.In various embodiments, when the voltage applied between the anode and cathode is lower than 3 or lower, 2.9 or lower, 2.8 or lower, 2.7 or lower, 2.6 or lower, 2.5 or lower, 2.4 or lower, 2.3 or lower, 2.2 or lower, 2.1 or lower, 2.0 or lower, 1.9 or lower, 1.8 or lower, 1.7 or lower, 1.6 or lower, 1.5 or lower, 1.4 or lower, 1.3 or lower, 1.2 or lower, 1.1 or lower, 1.0 or lower, 0.9 or lower, 0.8 or lower, 0.7 or lower, 0.6 or lower, 0.5 or lower, 0.4 or lower, 0.3 or lower, 0.2 or lower, or during 0.1V or lower, method 200 does not form gas at anode place, anode provides hydrogen simultaneously, proton is oxidized at this.Those of ordinary skill in the art will appreciate that, by not forming gas at anode place and providing hydrogen by anode to be oxidized at anode place, and by otherwise controlling the resistance in this system, hydroxyl ion can be produced by low voltage of the present invention in catholyte.

In various embodiments, method 200 comprises the step such as carbon dioxide 144 gas being imported catholyte 102 further; Such as settling with negative electrode 104 step carbon dioxide 144 being imported before or after catholyte catholyte contiguously; Such as to apply lower than 3V between negative electrode 104 and anode 108, or lower than 2V, or lower than 1.5V, or lower than 1V, or the step of voltage 134 lower than 0.5V; The step of hydrogen 136 is such as formed at negative electrode place; Such as at anode 108 place by hydroxide to form the step of proton; Such as by applying lower than 3V between the anode and cathode, or lower than 2V, or lower than 1.5V, or lower than 1V, or lower than the voltage of 0.5V, between anode and catholyte, form 1 when anode place does not form gas, 2,3,4,5,6,7,8,9,10,11,12,13, the step of 14pH unit or larger pH difference; By applying 3V or lower between the anode and cathode, or lower than 2V, or lower than 1.5V, or lower than 1.0V, or lower than the voltage of 0.5V, between the 4th electrolyte 116 and catholyte 102, form 1,2,3,4,5,6,7,8,9,10,11,12,13, the step of 14pH unit or larger pH difference; In catholyte 102, such as form hydroxyl ion, bicarbonate ion, carbanion and/or its step combined; In catholyte 102, such as form the step of NaOH, sodium acid carbonate or sodium carbonate; Proton is such as made to move to step the 4th electrolyte 116 through the second cation-exchange membrane 118 from anodolyte 106; Anion is such as made to move to step the 4th electrolyte 116 through anion-exchange membrane 120 from the 3rd electrolyte 110; Chlorion is such as made to move to step the 4th electrolyte 116 through anion-exchange membrane 120 from the 3rd electrolyte 110; In the 4th electrolyte, such as form the step of acid 148; In the 4th electrolyte, such as form the step of hydrochloric acid 148; Cation is such as made to migrate to the step of negative electrode 104 through the first cation-exchange membrane 112 from the 3rd electrolyte 110; Sodium ion is such as made to move to step catholyte 102 through the first cation-exchange membrane 112 from the 3rd electrolyte 110; Such as the hydrogen that negative electrode 104 place is formed is sent to the step being oxidized this gas at anode 108 place; Such as via flowing out the step of taking out catholyte 102 and supplementing catholyte via the inflow stream entering this catholyte; Such as supplement the 4th electrolytical step via outflow stream taking-up the 4th catholyte 116 with via the 4th electrolytical inflow stream.

With reference to Fig. 3 and 1, in another embodiment, method 300 comprises such as settles catholyte 102 contiguously and settles the step 302 of anodolyte 106 contiguously with anode 108 with negative electrode 104; Such as settle the step 304 that the 3rd electrolyte 110 is separated with catholyte 102 by the first cation-exchange membrane 112 to make it; Such as settle the step 306 that the 4th electrolyte 116 is separated by anion-exchange membrane 120 and the 3rd electrolyte 110 to make it and separated with anodolyte 106 by the second cation-exchange membrane 118; In catholyte 102, the step 308 of hydroxyl ion is such as formed by applying voltage between the anode and cathode.

In various embodiments, method 300 is as method 200, when the voltage applied between the anode and cathode is lower than 3,2.9,2.8,2.7,2.6,2.5,2.4,2.3,2.2,2.1,2.0,1.9,1.8,1.7,1.6,1.5,1.4,1.3,1.2,1.1,1.0,0.9,0.8,0.7,0.6,0.5,0.4,0.3,0.2 or 0.1V or lower, at anode 108, place does not form gas, anode provides hydrogen simultaneously, is oxidized to proton at this.Those of ordinary skill in the art will appreciate that, by not forming gas at anode place and providing hydrogen by anode in the oxidation of anode place, to produce hydroxyl ion with voltage of the present invention in catholyte.In various embodiments, the method 300 be combined with the system of Fig. 1 comprises further and between anode 108 and negative electrode 104, such as applies voltage to prevent from being formed at anode place the step of gas such as oxygen or chlorine; In catholyte 102, such as form the step of the mixture of bicarbonate ion, carbanion or bicarbonate radical and carbanion; Such as in the supply of anode 108 place and the step of oxidizes hydrogen gas; Apply the voltage of 3,2.9,2.8,2.7,2.6,2.5,2.4,2.3,2.2,2.1,2.0,1.9,1.8,1.7,1.6,1.5,1.4,1.3,1.2,1.1,1.0,0.9,0.8,0.7,0.6,0.5,0.4,0.3,0.2 or 0.1V or lower between a cathode and an anode; Such as form hydrogen at negative electrode 104 place; Such as at anode place by oxidation of hydrogen to form the step of proton at anode place; Such as when anode place does not form gas between anodolyte and catholyte formed 1,2,3,4,5,6,7,8,9,10,11,12,13,14pH unit or larger pH difference step; Such as when anode place does not form gas the 4th forming 1 between electrolyte and catholyte, 2,3,4,5,6,7,8,9,10,11,12,13, the step of pH gradient of 14pH unit or larger pH difference; In catholyte 102, such as form the step of the mixture of sodium carbonate, sodium acid carbonate or sodium carbonate and sodium acid carbonate; Proton is such as made to move to step the 4th electrolyte 116 through the second cation-exchange membrane 118 from anodolyte 106; Anion is made to move to step the 4th electrolyte 116 through anion-exchange membrane from the 3rd electrolyte 110; Chlorion is such as made to move to step the 4th electrolyte 116 through anion-exchange membrane 120 from the 3rd electrolyte 110; In the 4th electrolyte, such as form the step of acid 148; In the 4th electrolyte, such as form the step of hydrochloric acid 148; Cation is such as made to move to step catholyte 102 through the first cation-exchange membrane 112 from the 3rd electrolyte 110; Sodium ion is such as made to move to step catholyte 102 through the first cation-exchange membrane 112 from the 3rd electrolyte 110; The hydrogen 136 such as making negative electrode 104 place be formed circulates with the step be oxidized at anode 108 place; At least part of catholyte 102 is such as made to be recycled to step the inflow stream of this catholyte from flowing out stream; Part the 4th electrolyte 116 is such as made to be recycled to from flowing out stream the step flowed into stream.

In various embodiments, when anode place does not form gas, when the voltage applied between the anode and cathode lower than 3.0,2.9,2.8,2.7,2.6,2.5,2.4,2.3,2.2,2.1,2.0,1.9,1.8,1.7,1.6,1.5,1.4,1.3,1.2,1.1,1.0,0.9,0.8,0.7,0.6,0.5,0.4,0.3,0.2,0.1V or lower time, produce bicarbonate ion and carbanion.In various embodiments, the method be applicable to in batches, semi-batch or continuous operation mode extract the acid in catholyte and the 4th electrolyte at least partially and supplement back this system.

With reference to Fig. 1, when applying voltage between the anode and cathode, in this catholyte, forming hydroxyl ion or carbonate and/or bicarbonate ion, therefore regulate the pH value of this catholyte.In one embodiment, when applying 0.1V or lower between the anode and cathode, 0.2V or lower, 0.4V or lower, 0.6V or lower, 0.8V or lower, 1.0V or lower, 1.5V or lower, or 2.0V or lower, such as, during the voltage of 0.8V or lower, the pH value of this catholyte solution improves; In another embodiment, when applying 0.01 to 2.5V between the anode and cathode, or 0.01V to 2.0V, or 0.1V to 2.0V, or 0.1 to 2.0V, or 0.1V to 1.5V, or 0.1V to 1.0V, or 0.1V to 0.8V, or 0.1V to 0.6V, or 0.1V to 0.4V, or 0.1V to 0.2V, or 0.01V to 1.5V, or 0.01V to 1.0V, or 0.01V to 0.8V, or 0.01V to 0.6V, or 0.01V to 0.4V, or 0.01V to 0.2V, such as, or during the voltage of 0.01V to 0.1V, 0.1V to 2.0V, the pH value of this catholyte improves; In still another embodiment, when applying the voltage of about 0.1 to 1V between the anode and cathode, the pH value solution of this catholyte improves.With 0.1V to 0.8V between electrode; 0.1V to 0.7V; 0.1 to 0.6V; 0.1V to 0.5V; 0.1V to 0.4V; Similar results can be realized with the voltage of 0.1V to 0.3V.

The example results realized with native system is summarized in table 1 below.Use 270cm ²20-order Ni net (gauze) is as negative electrode and 50cm ²100-order Pt net, as anode, carries out running for 24 hours several times, is at room temperature wherein 20 ml/min by hydrogen stream to the flow control of anode, applies various voltage between the anode and cathode simultaneously.Solartron ^tMpotentiostat is used for electrochemical measurement, and selects respectively from GMbH ^tMthe PC Acid of Membranes of Germany and PC SK amberplex are as anion-exchange membrane and cation-exchange membrane.

Summary analyzed by table 1.24 hour

Applied voltage	Anion-exchange membrane	Cation-exchange membrane	Initial anode pH	Final anode pH	Initial negative electrode pH	Final negative electrode pH	Negative electrode pH changes
								1.0	PC Acid	PC SK	5.87	1.13	9.75	12.44	2.69
1.0	PC Acid	PC SK	4.68	2.03	9.20	12.43	3.23
								1.0	PC Acid	PC SK	3.25	2.02	9.98	11.33	1.35

Such as, in a particular embodiment, when applying 3V or lower between the anode and cathode, 2.9V or lower, or 2.5V or lower, or during the voltage of 2V or lower, it is poor that the method and system can produce the pH being greater than 0.5pH unit between Anolyte solution and catholyte solution, and these two kinds of electrolyte solutions are such as separated by one or more amberplex.In some embodiments, when applying the voltage of 0.1V or lower between the anode and cathode, the method and system can produce and be greater than 1.0pH unit between the first electrolyte solution and the second electrolyte solution, or 2pH unit, or 4pH unit, or 6pH unit, or 8pH unit, or 10pH unit, or 12pH unit, or the pH of 14pH unit is poor, wherein the first electrolyte solution contacts anode and the second electrolyte solution contacts negative electrode, and these two kinds of electrolyte solutions are such as separated by one or more amberplex.In some embodiments, the invention provides the system producing the pH difference being greater than 2.0pH unit when can apply the voltage of 0.2V or lower between the anode and cathode between the first electrolyte solution and the second electrolyte solution, wherein the first electrolyte solution contacts anode and the second electrolyte solution contacts negative electrode, and these two kinds of electrolyte solutions are such as separated by one or more amberplex.

In other embodiments, when applying the voltage of 0.4V or lower between the anode and cathode, it is poor that the method and system can produce the pH being greater than 4.0pH unit between the first electrolyte solution and the second electrolyte solution, wherein the first electrolyte solution contacts anode and the second electrolyte solution contacts negative electrode, and these two kinds of electrolyte solutions are such as separated by one or more amberplex.In some embodiments, the invention provides the system producing the pH difference being greater than 6pH unit when can apply the voltage of 0.6V or lower between the anode and cathode between the first electrolyte solution and the second electrolyte solution, wherein the first electrolyte solution contacts anode and the second electrolyte solution contacts negative electrode, and these two kinds of electrolyte solutions are such as separated by one or more amberplex.In some embodiments, the invention provides the system producing the pH difference being greater than 8pH unit when can apply the voltage of 0.8V or lower between the anode and cathode between the first electrolyte solution and the second electrolyte solution, wherein the first electrolyte solution contacts anode and the second electrolyte solution contacts negative electrode, and these two kinds of electrolyte solutions are such as separated by one or more amberplex.In a particular embodiment, the invention provides the system producing the pH difference being greater than 8pH unit when can apply the voltage of 1.0V or lower between the anode and cathode between the first electrolyte solution and the second electrolyte solution, wherein the first electrolyte solution contacts anode and the second electrolyte solution contacts negative electrode, and these two kinds of electrolyte solutions are such as separated by one or more amberplex.In some embodiments, the invention provides the system producing the pH difference being greater than 10pH unit when can apply the voltage of 1.2V or lower between the anode and cathode between the first electrolyte solution and the second electrolyte solution, wherein the first electrolyte solution contacts anode and the second electrolyte solution contacts negative electrode, and these two kinds of electrolyte solutions are such as separated by one or more amberplex.

Those of skill in the art will recognize that voltage do not need keep constant, when these two kinds of electrolytical pH are identical or pH close to time, the voltage applied between the anode and cathode can be very low, such as 0.05V or lower, along with pH difference improves, can improve voltage on demand.Thus, the production of required pH difference or hydroxyl ion, carbanion and bicarbonate ion can be realized with minimum average B configuration voltage.Therefore, in some embodiments described in the last period, this average voltage can be lower than 80%, 70%, 60%, or lower than in the last period of 50% to the voltage that specific embodiments provides.

In various embodiments with reference to Fig. 1, the hydrogen guiding anode 108 that negative electrode 104 place is formed.Be not subject to any theory, but it is believed that hydrogen adsorption and/or absorb in anode also subsequently at anode place oxidation formation proton.

In some embodiments, in the partial routine of the method that electrolyte contacts with amberplex, from this electrolyte solution, bivalent cation is removed, such as magnesium or calcium wherein.This is the fouling in order to prevent film, if necessary for certain films.Therefore, in various embodiments, when electrolyte solution to contact with amberplex any survey the time (appreciable time) time, bivalent cation total concentration in this electrolyte solution is lower than 0.06 mol/kg of solution, or lower than 0.06 mol/kg of solution, or lower than 0.04 mol/kg of solution, or lower than 0.02 mol/kg of solution, or lower than 0.01 mol/kg of solution, or lower than 0.005 mol/kg of solution, or lower than 0.001 mol/kg of solution, or lower than 0.0005 mol/kg of solution, or lower than 0.0001 mol/kg of solution, or lower than 0.00005 mol/kg of solution.

Carbon dioxide is being dissolved in the embodiment in catholyte, is removing deprotonation along with from catholyte, more carbon dioxide can be dissolved to form bicarbonate radical and/or carbanion.According to the pH of this catholyte, as fully understood in this area and as shown in above-mentioned carbonate species formation figure, this balance is shifted to bicarbonate radical or shifted to carbonate.In these embodiments, remove speed according to the proton compared with introducing speed with carbon dioxide, the pH of this catholyte solution may reduce, and keeps identical or improves.Recognize, do not form hydroxyl ion, carbonate or bicarbonate ion in these embodiments, or hydroxyl ion, carbonate, bicarbonate radical may not formed a period but be formed in another period.

In another embodiment, native system and method and carbonate and/or bicarbonate settling system (not shown) integrated, wherein bivalent cation solution causes when adding in this catholyte forming dicovalent carbon hydrochlorate and/or bicarbonate compound, the sediment of such as calcium carbonate or magnesium carbonate and/or their bicarbonate.In various embodiments, the dicovalent carbon hydrochlorate of this precipitation and/or bicarbonate compound are used as construction material, such as cement and gathering materials, the U.S. Patent application no.12/126 of the common transfer that 23 days Mays in 2008 as the full text is incorporated herein by reference submit to, described in 776.

In another embodiment, native system and method and mineral and/or material dissolves and recovery system (not shown) integrated, acid 4th electrolyte solution 116 or alkaline cathode electrolyte 102 is wherein used to dissolve the mineral being rich in calcium and/or magnesium, such as serpentine or olivine, or waste material, such as flying dust, red soil etc., to form the bivalent cation solution for precipitated carbonate as described herein and/or bicarbonate.In various embodiments, the dicovalent carbon hydrochlorate of this precipitation and/or bicarbonate compound are used as construction material, such as cement and gathering materials, the U.S. Patent application no.12/126 of the common transfer that 23 days Mays in 2008 as the full text is incorporated herein by reference submit to, described in 776.

In another embodiment, native system and method and other composition such as sulphur gas for sequestration of carbon dioxide and industrial waste gas, oxides of nitrogen gas, the industrial waste gas treatment system (not shown) of metal and particulate is integrated, the U.S. Patent application no.12/344 of the common transfer that the 24 days December in 2008 wherein as the full text is incorporated herein by reference submits to, by making flue gas and comprising the solution of bivalent cation and comprise hydroxyl described in 019, this catholyte contact of bicarbonate radical and/or carbanion, precipitation divalent cation and/or bicarbonate.The sediment of this carbonate and bicarbonate that comprise such as calcium and/or magnesium is used as construction material in various embodiments, such as be used as cement and gather materials, the U.S. Patent application no.12/126 of the common transfer that 23 days Mays in 2008 as the full text is incorporated herein by reference submit to, described in 776.

In another embodiment, native system and method and water-based desalination system (not shown) integrated, wherein the 3rd of native system the electrolytical partially desalted water 150 is used as the feed water of this desalination system, the U.S. Patent application no.12/163 of the common transfer that the 27 days June in 2008 as the full text is incorporated herein by reference submits to, described in 205.

In another embodiment, native system and method and carbonate and/or bicarbonate solution disposal system (not shown) integrated, wherein, this system manufacture comprises slurry or the suspension of carbonate and/or bicarbonate, but not by making the solution of bivalent cation and the first electrolyte solution contacts manufacture sediment to form sediment.In various embodiments, this slurry/suspension is thrown aside in the place making it maintain a long-term stability, the U.S. Patent application no.12/344 that the 24 days December in 2008 such as the full text is incorporated herein by reference submits to, described in 019, being thrown aside by this slurry/suspension is enough to make indefinitely this slurry to keep in the ocean of the stable degree of depth being in temperature and pressure.

Although shown and described some embodiments of this system and method herein, it should be apparent to those skilled in the art that these embodiments as an example but not provide as restriction.Those skilled in the art can expect variation within the scope of the appended claims, amendment and substitute.

Claims

1. electro-chemical systems, it comprises:

Comprise the first battery with the catholyte of cathode contacts,

Wherein this negative electrode is through constructing to produce hydroxyl ion and hydrogen,

Wherein this first battery is effectively connected to a system, and described system is selected from and is configured to carbon dioxide is transported to the carbon dioxide gas body conveying system in the first battery holding catholyte; Or be configured to carbon dioxide absorption to the gas absorption system in the first battery holding catholyte;

Wherein this catholyte comprises bicarbonate ion, and wherein to have the pH of 6-12 poor for anodolyte and catholyte;

Comprise the second battery with the anodolyte of positive contact, wherein this anode structure becomes hydrogen-oxygen is changed into proton;

Be configured to the gas transfer system of gas from cathode guide anode;

Comprise the 3rd electrolytical 3rd battery separated by the first amberplex and this catholyte;

Comprise the 4th electrolytical 4th battery separated by the second amberplex and this anodolyte;

Separate the 3rd amberplex of the 3rd and the 4th battery, and

This special cell voltage of energy striding across anode and negative electrode is less than 0.8V.

2. the system of claim 1, wherein the first amberplex comprises cation-exchange membrane; Second amberplex comprises cation-exchange membrane; And the 3rd amberplex comprises anion-exchange membrane.

3. the system of claim 1, wherein this gas transfer system is configured to hydrogen to import in anodolyte, or leads on anode, or its combination, to be oxidized this gas at anode place.

4. the system of claim 1, wherein this carbon dioxide gas body conveying system can be connected to the industrial waste gas streaming system comprising burning gases effectively.

5. the system of claim 1, wherein this carbon dioxide gas body conveying system can be connected to the power plant or cement plant gas extraction system that fossil fuels effectively.

6. the system of claim 1, forms hydroxyl ion when anode place does not form gas when wherein this system is through constructing to apply voltage in-between the electrodes in catholyte.

7. the system of claim 6, comprises through structure further with the voltage source applying the voltage lower than 0.6V between the anode and cathode.

8. the system of claim 1, forms hydroxyl ion, bicarbonate ion and/or carbanion when anode place does not form gas when wherein this system is through constructing to apply voltage in-between the electrodes in catholyte.

9. the system of claim 1, wherein this system is through constructing to remove sodium ion and chlorion when anode place does not generate gas from the 3rd electrolyte.

10. the system of claim 1, wherein this system is through constructing to form acid solution when anode place does not generate gas in the 4th electrolyte.

The system of 11. claims 1, comprises further and is applicable to make the catholyte of part to be recycled to the circulatory system the inflow stream of catholyte from flowing out stream.

The system of 12. claims 1, comprises further for making the 4th electrolyte of part be recycled to the 4th electrolytical circulatory system flowed into stream from flowing out stream.

The system of 13. claims 1, wherein this system be applicable in batches, semi-batch or Continuous Flow operation.

The system of 14. claims 1, wherein this system is applicable to Continuous Flow operation.

The system of 15. claims 1, wherein this catholyte comprises the carbon dioxide of dissolving.

The system of 16. claims 15, wherein this catholyte comprises hydroxyl, bicarbonate ion and/or carbanion.

The system of 17. claims 15, wherein this catholyte comprises sodium acid carbonate, sodium carbonate or its combination.

The system of 18. claims 1, wherein the 4th electrolyte comprises proton and chlorion.

The system of 19. claims 1, wherein this anodolyte comprises proton.

20. electrochemical methods, it comprises:

With cathode contacts settle catholyte, wherein negative electrode produces hydroxyl ion and hydrogen;

With positive contact settle anodolyte, hydrogen-oxygen is changed into hydrogen ion by its Anodic;

Settle the 3rd electrolyte separated by the first amberplex and this catholyte;

Settle the 4th electrolyte being separated by the 3rd amberplex and the 3rd electrolyte and separated by the second amberplex and this anodolyte;

By the hydrogen guiding anode produced at negative electrode;

The dioxide solution guiding of the carbonated industrial waste gas of bag or dissolving is held in the first battery of catholyte;

In catholyte, bicarbonate ion is changed into carbanion and between anodolyte and catholyte, produce the pH of 6-12 poor; And stride across this special cell voltage of energy that negative electrode and anode apply to be less than 0.8V.

The method of 21. claims 20, wherein the first amberplex comprises cation-exchange membrane; Second amberplex comprises cation-exchange membrane; And the 3rd amberplex comprises anion-exchange membrane.

The method of 22. claims 20, does not wherein form gas at anode place.

The method of 23. claims 20, wherein with cathode contacts settle catholyte before or after carbon dioxide is imported catholyte.

The method of 24. claims 20, comprises the voltage applied between a cathode and an anode lower than 0.6V.

The method of 25. claims 20, is included in catholyte and forms hydroxyl ion, bicarbonate ion, carbanion and/or its combination.

The method of 26. claims 20, is included in catholyte and forms NaOH, sodium acid carbonate or sodium carbonate.

The method of 27. claims 20, comprises and proton is moved to the 4th electrolyte through the second cation-exchange membrane from anodolyte.

The method of 28. claims 27, comprises and anion is moved to the 4th electrolyte through anion-exchange membrane from the 3rd electrolyte.

The method of 29. claims 28, comprises and chlorion is moved to the 4th electrolyte through anion-exchange membrane from the 3rd electrolyte.

The method of 30. claims 29, is included in the 4th electrolyte and forms acid.

The method of 31. claims 29, is included in the 4th electrolyte and forms hydrochloric acid.

The method of 32. claims 28, comprises and makes cation migrate to negative electrode from the 3rd electrolyte through the first cation-exchange membrane.

The method of 33. claims 20, comprises and sodium ion is moved to catholyte through the first cation-exchange membrane from the 3rd electrolyte.

The method of 34. claims 20, comprises and catholyte is recycled to the inflow stream of this catholyte from outflow stream.

The method of 35. claims 20, comprises and the 4th catholyte is recycled to the 4th electrolytical inflow stream from outflow stream.

The system of 36. claims 10, comprises the material dissolves system being effectively connected to electro-chemical systems further, and this material dissolves system is through constructing to utilize acid to dissolve the material and generation bivalent cation solution that are rich in calcium and/or magnesium.